Hydrogen Evolution on Binary and Ternary Cobalt Alloys Deposited With Superimposed Magnetic Field

The article presents results of electrodeposition of Co-Mo Co-Mo-C alloys in a magnetic field characterized by low overvoltage of hydrogen evolution.Addition of molybdenum and carbon was to lower the values of overvoltage of hydrogen evolution on cobalt.The influence of bath pH,bath composite,current density and magnetic field with different orientation on the deposits composition,structure and overpotential for hydrogen evolution reaction(HER)was determined.Electrocatalytic properties of the obtained alloy coatings within the range of hydrogen evolution were tested in a concentrated NaOH solution.The comparison of electrocatalytic properties of Co-Mo alloys with properties of Co-Mo-C ones enabled determining the influence of carbon presence in cathodic deposits on the overpotential values for hydrogen evolution.     

The influence of oxidizing agents on water extracts of rye flour

The main constituents of rye flour extracts are proteins and pentosans. After cross-linking under the action of oxidizing agents those components are able to bind much more water than in their native (prior to modifications) state. As a consequence rheological properties of extract are changed.It was observed that kinematic viscosity of water extract of rye flour decreases rapidly with time. The reason for this behavior could be high enzymatic activity of flour extract.It was also found that the addition of hydrogen peroxide in the absence of additional peroxidase (which is naturally present in 1:9 or 1:1 water extracts of flour) causes the greatest increase in viscosity, due to the cross-linking of soluble polymers. Moreover after the addition of H₂O₂ to water extracts strong gels were obtained, which were characterized by tan δ = 0.5 (tan δ < 1). Moreover G′ was independent of frequency, which also suggests cross-linking of the pentosans.The addition of ascorbic acid, which is known to act preferably on gluten proteins, to 1:9 or 1:1 flour extracts had only a little effect on viscosity. In this case the values of tan δ = 0.9 were close to 1, which is typical for a weak gel.The application of inactivated rye flour extract, containing mainly proteins and pentosans, proved stronger effect of H₂O₂ in comparison to ascorbic acid on polymer cross-linking, but only after the addition of peroxidase. The gel obtained with H₂O₂ and peroxidase was also characterized by low tan δ = 0.4.The results indicate, that pentosans are the main subject of cross-linking reactions in rye flour water extracts.     

Modification of Fe and Al elemental powders’ sintering with addition of magnesium and magnesium hydride

An attempt to modify sintering of iron and aluminium elemental powders with use of small additions of Mg and MgH₂ was presented in this paper. The kinetics of such modified sintering was investigated using DSC technique, XRD analysis and SEM observations. Significant changes in the mechanism of exothermal formation reaction of Fe–Al intermetallic phases in compositions doped with magnesium and its hydride was observed. Initiation temperature of Self-propagating High-temperature Synthesis (SHS) reaction was pronouncedly shifted to lower value as compared with undoped composition. Influence of additions on the SHS reaction kinetics parameters was also calculated with use of the JMA model and changes of the Avrami exponent value of specific phase formation was noticed. Positive effect of MgH₂ addition on partial homogeneity of final product was also studied.     

The influence of electron beam irradiation,plastic deformation,and re‐irradiation on crystallinity degree,mechanical and sclerometric properties of GUR 1050 used for arthroplasty

The article describes the influence of an electron beam irradiation (I), plastic deformation (D), and re‐irradiation (R) on the properties of ultrahigh molecular weight polyethylene (GUR 1050). It was found that the modification through irradiation entailed a gradual increase in the degree of crystallinity (after irradiation–I). After plastic deformation and re‐irradiation (IDR) the degree of crystallinity decreases which had a direct influence on the mechanical properties. The polymer irradiation only (technique I) resulted in an increase in the maximum stress as compared with the material in the initial state. The application of deformation and re‐irradiation (technique IDR) allowed increasing the deformation resistance by more than 40%. Moreover, the irradiation with an electron beam resulted in the increase in hardness (H) and Young's modulus (E) proportionally to the applied irradiation dose and in the reduction of total indentation work (W_tot) and its components. After deformation and re‐irradiation the polyethylene hardness went down. The application of technique (I) caused an improvement to the material abrasion resistance (reduction of parameter PD–working scratch depth) with the increasing irradiation dose. The introduction of deformation and re‐irradiation did not have a material impact on parameter (PD) increasing at the same time elastic properties of UHMWPE (increase in parameter NPS–elastic recovery). Modification IDR has changed the wear mechanism (β) toward ploughing and has increased the abrasion‐resistance index (W_β) and also significantly reduced the coefficient of friction (μ) of GUR 1050. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43683.     

Artificial Maturation of the Highly Active Heterodimeric [FeFe] Hydrogenase from Desulfovibrio desulfuricans ATCC 7757

Hydrogenases catalyze the reduction of protons and oxidation of molecular hydrogen with high turnover frequencies and low overpotentials under ambient conditions. The heterodimeric [FeFe] hydrogenase from Desulfovibrio desulfuricans has an exceptionally high activity, and can be purified aerobically in an oxygen-stable inactive state. Recently, it was demonstrated that monomeric [FeFe] hydrogenases produced recombinantly in Escherichia coli can be artificially maturated by simply incubating the inactive “apo” enzymes with the synthetic [2Fe] cofactor mimic [Fe₂(adt)(CO)₄(CN)₂]²⁻. Here, we use the same technique to produce the heterodimeric “apo” hydrogenase from D. desulfuricans in E. coli with a high yield and purity, and maturate the “apo” enzyme with [Fe₂(adt)(CO)₄(CN)₂]²⁻ to generate fully active “holo” enzyme. Interestingly, the rate of the artificial maturation process with D. desulfuricans is significantly slower than that for all other hydrogenases tested so far. The artificially maturated enzyme is spectroscopically and electrochemically identical to the native enzyme and shows high rates of hydrogen production (3700 s⁻¹) and hydrogen oxidation (63,000 s⁻¹). We expect that our highly efficient production method will facilitate future studies of this enzyme and other related [FeFe] hydrogenases from Desulfovibrio species.     

Clickable poly(ionic liquid)s for modification of glass and silicon surfaces

Covalent attachment of poly(ionic liquid)s (PILs) by click chemistry on glass or silicon (Si) surfaces was performed. Poly[1-(4-vinylbenzyl)-3-butylimidazolium bis(trifluoromethylsulfonyl)imide] (polyVBBI⁺Tf₂N⁻), and copolymers of polyVBBI⁺Tf₂N⁻ with fluorescein O-methacrylate were synthesized by conducting an atom transfer radical polymerization (ATRP) from initiators containing azide or thioacetate groups. The azide- and thiol-terminated PILs were then successfully grafted onto alkyne and alkene modified glass/Si wafers by thermal azide–alkyne cycloaddition and photoinitiated thiol-ene click reactions, respectively. The modified surfaces were characterized by contact angle measurements and ellipsometry. The fluorescent PIL functionalized surfaces showed strong fluorescence under UV irradiation. This procedure of tethering PILs to substrates also provides an easy way to change the surface hydrophilicity by replacing the anions in the grafted PILs. The present approach could be readily applied for surface modifications with other types of PILs or their copolymers to achieve different functionalities on various surfaces.     

Cavitation during deformation of semicrystalline polymers

Cavitation phenomenon is observed during deformation in many semicrystalline polymers above their glass transition temperature. Numerous voids (cavities) both nanometer and micrometer size are formed inside amorphous phase between lamellae during deformation of a polymer. The cavitation is observed only in tension, never during compression or shearing. Most often used methods of voids detection are: microscopies (SEM, TEM, AFM and light microscopy), small angle X-ray scattering and measurements of density. Usually the voids are detected close to yielding or at yielding, strongly suggesting that yielding is often caused by cavitation. However, there is a competition between two processes: breaking of amorphous phase leading to cavitation and plastic deformation of lamellar crystals. Which process occurs first depends on the relation between compliances of those two phases. If the crystals are weak and defected their deformation occurs (mostly by chain slips mechanism) without cavitation. If the crystals in a polymer are thick and more perfect then the barrier for their deformation, represented by shear yielding stress, is increased and the cavitation sets in first and yielding is determined by the stress needed for cavitation. Further deformation involves deformation of crystals due to rapid local change of stress around voids. The influence of different morphological factors: crystal thickness, crystallinity degree, arrangement of crystalline elements (e.g. in spherulites), morphology of amorphous phase (free volume, entanglements, tie molecules) were analyzed. Experimental factors, such as temperature of deformation and rate of deformation influence remarkably the formation of cavities. Cavitation is generated at points where a high local triaxial state of stress is developed. Triaxiality of stress can be amplified by a notch, even very mild notch with large radius of curvature stimulates generation of cavities. Evolution of nano-cavities into micro-cavities and change of their shapes with increasing deformation were evidenced by SAXS. Initially voids are oriented perpendicularly to deformation direction, however, with increasing elongation they become oriented along deformation direction. Stress whitening is visual sign of cavitation and is caused be light scattering either by microvoids or by assemblies of nanovoids.     

Hexokinase 2 Inhibition and Biological Effects of BNBZ and Its Derivatives: The Influence of the Number and Arrangement of Hydroxyl Groups

Hexokinase 2 (HK2), an enzyme of the sugar kinase family, plays a dual role in glucose metabolism and mediating cancer cell apoptosis, making it an attractive target for cancer therapy. While positive HK2 expression usually promotes cancer cells survival, silencing or inhibiting this enzyme has been found to improve the effectiveness of anti-cancer drugs and even result in cancer cell death. Previously, benitrobenrazide (BNBZ) was characterized as a potent HK2 inhibitor with good anti-cancer activity in mice, but the effect of its trihydroxy moiety (pyrogallol-like) on inhibitory activity and some cellular functions has not been fully understood. Therefore, the main goal of this study was to obtain the parent BNBZ (2a) and its three dihydroxy derivatives 2b–2d and to conduct additional physicochemical and biological investigations. The research hypothesis assumed that the HK2 inhibitory activity of the tested compounds depends on the number and location of hydroxyl groups in their chemical structure. Among many studies, the binding affinity to HK2 was determined and two human liver cancer cell lines, HepG2 and HUH7, were used and exposed to chemicals at various times: 24 h, 48 h and 72 h. The study showed that the modifications to the structures of the new BNBZ derivatives led to significant changes in their activities. It was also found that these compounds tend to aggregate and exhibit toxic effects. They were found to contribute to: (a) DNA damage, (b) increased ROS production, and (c) disruption of cell cycle progression. It was observed that, HepG2, occurred much more sensitive to the tested chemicals than the HUH7 cells; However, regardless of the used cell line it seems that the increase in the expression of HK2 in cancer cells compared to normal cells which have HK2 at a very low level, is a serious obstacle in anti-cancer therapy and efforts to find the effective inhibitors of this enzyme should be intensified.     

Investigating the Potential Use of Chemical Biopsy Devices to Characterize Brain Tumor Lipidomes

The development of a fast and accurate intraoperative method that enables the differentiation and stratification of cancerous lesions is still a challenging problem in laboratory medicine. Therefore, it is important to find and optimize a simple and effective analytical method of enabling the selection of distinctive metabolites. This study aims to assess the usefulness of solid-phase microextraction (SPME) probes as a sampling method for the lipidomic analysis of brain tumors. To this end, SPME was applied to sample brain tumors immediately after excision, followed by lipidomic analysis via liquid chromatography-high resolution mass spectrometry (LC-HRMS). The results showed that long fibers were a good option for extracting analytes from an entire lesion to obtain an average lipidomic profile. Moreover, significant differences between tumors of different histological origin were observed. In-depth investigation of the glioma samples revealed that malignancy grade and isocitrate dehydrogenase (IDH) mutation status impact the lipidomic composition of the tumor, whereas 1p/19q co-deletion did not appear to alter the lipid profile. This first on-site lipidomic analysis of intact tumors proved that chemical biopsy with SPME is a promising tool for the simple and fast extraction of lipid markers in neurooncology.